EP2132347B1 - Verfahren zur verarbeitung von cadmiumhaltigen feststoffen - Google Patents

Verfahren zur verarbeitung von cadmiumhaltigen feststoffen Download PDF

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Publication number
EP2132347B1
EP2132347B1 EP20070726637 EP07726637A EP2132347B1 EP 2132347 B1 EP2132347 B1 EP 2132347B1 EP 20070726637 EP20070726637 EP 20070726637 EP 07726637 A EP07726637 A EP 07726637A EP 2132347 B1 EP2132347 B1 EP 2132347B1
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European Patent Office
Prior art keywords
cadmium
solution
alkaline metal
aqueous
sulfate
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EP20070726637
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English (en)
French (fr)
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EP2132347A1 (de
Inventor
Abdelaâli KOSSIR
Philippe Cappelle
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Prayon Technologies
OCP SA
Original Assignee
Prayon Technologies
Centre dEtudes et de Recherches des Phosphates Mineraux CERPHOS
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Priority to PL07726637T priority Critical patent/PL2132347T3/pl
Publication of EP2132347A1 publication Critical patent/EP2132347A1/de
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B25/00—Phosphorus; Compounds thereof
    • C01B25/16—Oxyacids of phosphorus; Salts thereof
    • C01B25/18—Phosphoric acid
    • C01B25/234—Purification; Stabilisation; Concentration
    • C01B25/237—Selective elimination of impurities
    • C01B25/238—Cationic impurities, e.g. arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • C01F11/468—Purification of calcium sulfates
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B17/00—Obtaining cadmium
    • C22B17/04—Obtaining cadmium by wet processes
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
    • C22B7/006—Wet processes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to a method for treating cadmium solids comprising calcium sulphate anhydrite and / or hemihydrate having a cadmium content.
  • the Cd concerns several industries that can be mining, metal or other. It can be found especially during processes of treatment and / or recovery of phosphoric solutions, sulfuric, nitric, etc. From these solutions Cd can be recovered by co-crystallization with calcium sulfate in its anhydrite and / or hemihydrate form.
  • calcium sulphate hemihydrate obtained in certain processes for the manufacture of wet phosphoric acid may contain a high concentration of cadmium rendering it unfit for recovery or disposal treatments.
  • cadmium solids any solid phase containing cadmium, whether in the form of blocks, powder, agglomerates, or slurry, such as a filter cake.
  • a cadmium solid according to the invention may also naturally contain cadmium.
  • Processes for the purpose of treating this type of cadmium solids for the purpose of extracting cadmium have been known for some time. These processes involve digesting the cadmium solids with sulfuric acid having a concentration advantageously of the order of 0.1 M to 2 M and that at a temperature between 0 ° C and 30 ° C. Cadmium is released in solution in sulfuric acid while calcium sulphate is recrystallized (rehydrated) as a dihydrate (see, for example WO91 / 00244 ). This process has a very slow kinetics and requires, among other things, a duration of more than ten hours in a highly corrosive environment.
  • the object of the present invention is to develop a process for treating the cadmium solids in question which is rapid, while making the final recovery of cadmium easier.
  • this process must give rise to a solid cadmium concentrate with a high cadmium content and a reduced volume, which facilitates its deposition or recovery.
  • alkali metal sulphate sodium, potassium or lithium sulphate, in particular sodium sulphate, is especially contemplated.
  • Sodium sulfate can be used as a salt which is dissolved in an aqueous medium for extraction. It can be formed by mixing sulfuric acid and sodium hydroxide just before extraction or in situ in the digestion reactor.
  • the aqueous solution of alkali metal sulphate in particular sodium sulphate, may have a sulphate concentration which varies between 1% by weight and the solubility limit of the sulphate in water.
  • concentration of sodium sulphate in the aqueous solution for the extraction is advantageously between 5 and 15% by weight, preferably between 7 and 12% by weight, calculated on the basis of sulphate ions.
  • the extraction takes place in an aqueous medium having a solids content of between 0.5 and 50% by weight, advantageously between 15 and 30% by weight and preferably between 20 and 25% by weight.
  • the temperature of the extraction is maintained between 5 and 60 ° C, preferably between 5 and 30 ° C, preferably between 15 and 25 ° C.
  • the pH during the extraction is advantageously between 1 and 6, preferably between 3 and 6, that is to say at a value close to neutrality. Extraction is therefore carried out with rapid kinetics and in a very low corrosive environment, which facilitates handling and reduces investment and maintenance costs.
  • the aqueous alkali metal sulphate solution of the extraction may contain a complexing agent which promotes the passage and keeping in solution of the cadmium, which gives final calcium sulphate with a very low Cd content.
  • a complexing agent which promotes the passage and keeping in solution of the cadmium, which gives final calcium sulphate with a very low Cd content.
  • chlorides and fluorides for example calcium, sodium or other, EDTA (ethylenediamine tetraacetic acid), or any other anion generator capable of forming a complex with Cd.
  • EDTA ethylenediamine tetraacetic acid
  • the solid-liquid mixture is then separated by any appropriate separation technique: decantation, filtration, centrifugation, etc.
  • the solid residue is formed of exceptionally decadmized calcium sulfate dihydrate, which may have a Cd content of less than 30 ppm, especially 10 ppm and preferably 3 ppm. This gypsum can be stored or put on the market, as it can be partially recycled in the process, as will be seen later, possibly even after storage.
  • the process comprises recovering cadmium from said aqueous phase containing alkali metal sulphate and cadmium in solution and optionally recycling an aqueous solution of decadminated alkali metal sulphate. in the extraction step.
  • This recovery can be carried out according to any appropriate chemical or electrochemical method, known to those skilled in the art, or by ion exchange.
  • a precipitation of cadmium sulfides or soda Preferably, a precipitation of cadmium sulfides or soda.
  • said recovery comprises an addition of alkali metal sulfide to said aqueous phase containing alkali metal sulphate and cadmium in solution, a precipitation of a solid phase constituted mainly of cadmium sulphide, and a separation of this solid phase from an aqueous solution of decadminated alkali metal sulphate.
  • This simple process allows the cadmium to be recovered in the form of a stable, low volume concentrate based on cadmium sulphide.
  • the aqueous liquid phase based on alkali metal sulfate, preferably sodium, which has been decadminated, can now advantageously be recycled to the extraction step.
  • the cadmium solids to be treated according to the invention may be derived from a decadmination process of an aqueous solution containing cadmium, comprising a co-crystallization therein of cadmium with calcium sulphate. anhydrite and / or hemihydrate.
  • the aqueous solution is for example phosphoric, sulfuric or phosphosulfuric in nature, but it may also contain other components, for example nitric acid, or mixtures of acids.
  • the decadmination process provides for the introduction of a calcium compound capable of forming in this solution a precipitate of calcium sulfate anhydrite and / or hemihydrate which will co-precipitate the cadmium.
  • calcium sulfate can be introduced. This can be prepared prior to introduction from sulfuric acid and a calcium compound, or even in situ in the decadmination reactor. It is also possible to recycle said solid phase based on sulphate cadmium-depleted calcium dihydrate in said co-crystallization as said calcium compound.
  • the treatment of a cadmium rejection resulting from a process for the preparation of phosphoric acid obtained by the wet process has been illustrated.
  • the 45-60 wt% phosphoric acid P 2 O 5 aqueous solution was produced from a cadmium ore and thus contains a high cadmium content, which would desirably be disposed of.
  • the aqueous solution of phosphoric acid decadmier is introduced in 1 in a cocrystallization tank 2 with a calcium compound which is fed in 3 and which must allow precipitation of calcium sulfate.
  • the phosphoric acid to be treated was obtained by phospho-sulfuric attack of the ore.
  • the calcium compound to be introduced at 3 into the co-crystallization tank 2 is a calcium sulphate, for example gypsum.
  • a co-crystallization of cadmium in the crystal lattice of calcium sulphate is observed.
  • the co-crystallization sludge, rich in cadmium is then transferred via line 4 to a filtration device 5, where it can be filtered and washed with a wash water introduced at 6.
  • the filtrate is formed of a deeply decadmized phosphoric acid which may have a Cd content of up to 2 ppm or less. This filtrate is evacuated in 7.
  • the filter cake has a cadmium content of 1042 ppm.
  • a decadmination tank 9 into which an alkali metal solution is introduced.
  • an alkali metal solution is introduced.
  • it is a solution of Na 2 SO 4 at a concentration of the order of 10% by weight, calculated on the basis of sulfate ions.
  • the specimenadmiation takes place at a temperature of 19 ° C and a pH of the order of 4.88.
  • the solids content in the medium is of the order of 21.9% by weight.
  • the filter cake is allowed to digest, then the decadmation sludge is transferred via line 11 to a filtration device 12, where it can be filtered and washed with a washing water introduced at 13.
  • the filter cake is formed of a solid cadmium-free release, which is formed in the present example of calcium sulfate dihydrate. Because of its high degree of purity, this calcium sulfate dihydrate can be transferred to a storage (not shown) in 14 for subsequent industrial exploitation. It is also possible to recycle it at least partially as the calcium compound to be introduced at 3 into the co-crystallization tank 2.
  • the filtrate is formed of a sodium sulphate solution containing cadmium in solution.
  • it is introduced through line 16 into a precipitation vessel 17, into which a sulfide, for example NaHS, is introduced at 18.
  • a solid phase based on cadmium sulphide precipitates.
  • the sulphide precipitation sludge is then transferred to a solid / liquid separation device 20.
  • the filter cake discharged at 21 is formed of a solid rejection based on cadmium sulphide, where the Cd concentration can be of the order of 32% by weight. Cadmium is therefore very concentrated in a reduced volume of solid material which represents a significant advantage for the disposal of the cadmium rejection.
  • the filtrate is a solution of sodium sulphate substantially completely decadminated. It has less than 1 ppm of Cd. It can be evacuated, or advantageously at least partially recycled through line 22 to the inlet 10 of decadming tank 9.
  • the extraction efficiency of the cadmium is observed on examination of the solid discharged from the filtration device 12 and the filtrate passing through the pipe 16. As can be seen the yield extraction is ideal in the process according to the invention, and this in a short time.
  • a cadmium solid having a content of 321 ppm Cd was contacted with a solution of sodium sulfate prepared by neutralization of sulfuric acid with sodium hydroxide.
  • the reaction took place in a stirred reactor in the presence of sodium sulfate at a concentration of 8.21% by weight of SO 4 .
  • the separated solid contained only 1 ppm Cd.
  • Precipitation of Cd in solution by addition of NaHS made it possible, after filtration, to obtain a solid phase consisting mainly of cadmium sulphide and where the Cd concentration is 32%.
  • the decadminated sodium sulfate solution is less than 1 ppm Cd.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Extraction Or Liquid Replacement (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • Removal Of Specific Substances (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Processing Of Solid Wastes (AREA)

Claims (15)

  1. Verfahren zur Behandlung cadmiumhaltiger Feststoffe, die Calciumsulfat-Anhydrit und/oder -Halbhydrat aufweisen, welche(s) einen Gehalt an Cadmium aufweist/aufweisen,
    dadurch gekennzeichnet, dass es Folgendes umfasst
    - eine Cadmiumextraktion, ausgehend von den cadmiumhaltigen Feststoffen, indem diese mit einer wässrigen Alkalimetallsulfatlösung in Kontakt gebracht werden, und
    - eine fest/flüssig-Trennung zwischen einer Feststoffphase auf Basis von Calciumsulfat-Dihydrat mit einem Cadmiumgehalt, der gegenüber dem Cadmiumgehalt des Calciumsulfat-Anhydrits und/oder Halbhydrats verringert ist, und einer wässrigen Phase, die Alkalimetallsulfat und Cadmium in Lösung enthält.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die wässrige Alkalimetallsulfatlösung eine Konzentration an Sulfat aufweist, die im Bereich von 1 Gewichts% und dem Grenzwert der Wasserlöslichkeit des Alkalimetallsulfats liegt.
  3. Verfahren nach einem der Ansprüche 1 und 2, dadurch gekennzeichnet, dass die Extraktion in einem Milieu erfolgt, das einen Feststoffgehalt im Bereich von 0,5 bis 50 Gewichts% aufweist.
  4. Verfahren nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die Extraktion unter Aufrechterhaltung einer Temperatur im Bereich von 5 bis 60 °C, vorzugsweise von 5 bis 30 °C, erfolgt.
  5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Extraktion bei einem pH-Wert im Bereich von 1 bis 6, vorzugsweise von 3 bis 6, erfolgt.
  6. Verfahren nach einem beliebigen der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die cadmiumhaltigen Feststoffe aus einem Verfahren zum Entfernen von Cadmium aus einer cadmiumhaltigen wässrigen Lösung stammen, wobei eine co-Kristallisation von Cadmium mit Calciumsulfat-Anhydrit und/oder -Halbhydrat erfolgt.
  7. Verfahren nach Anspruch 6, dadurch gekennzeichnet, dass das Cadmiumentfernungsverfahren auf eine phosphor-, schwefel-, phosphor- und schwefel-, oder stickstoffhaltige wässrige Lösung oder auf eine Lösung, die aus einer Mischung zweier oder mehrerer Säuren besteht, insbesondere auf eine cadmiumhaltige Phosphorsäurelösung, angewendet wird.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die fest/flüssig-Trennung durch Dekantieren, Filtrieren oder Zentrifugieren erfolgt.
  9. Verfahren nach einem beliebigen der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Festphase auf Basis von Calciumsulfat-Dihydrat mit einem verringerten Cadmiumgehalt zwischengelagert und/oder wiederverwertet wird.
  10. Verfahren nach einem beliebigen der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die wässrige Alkalimetallsulfatlösung, welche für den Extraktionsschritt verwendet wird, mindestens ein Komplexierungsmittel enthält, welches begünstigend darauf wirkt, dass das Cadmium in Lösung geht und in Lösung verbleibt.
  11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass es eine Rückgewinnung des Cadmiums umfasst, und zwar ausgehend von der wässrigen Phase, die Alkalimetallsulfat und Cadmium in Lösung enthält, sowie möglicherweise eine Wiederverwertung einer wässrigen Alkalimetallsulfatlösung, aus welcher im Extraktionsschritt das Cadmium entfernt wurde.
  12. Verfahren nach Anspruch 11, dadurch gekennzeichnet, dass die Rückgewinnung auf chemischem oder elektrochemischem Wege oder durch Ionenaustausch erfolgen kann.
  13. Verfahren nach Anspruch 12, dadurch gekennzeichnet, dass die Rückgewinnung auf chemischem Wege einen Zusatz von Alkalimetallsulfid zu der wässrigen Phase, die Alkalimetallsulfat und Cadmium in Lösung enthält, eine Ausfällung einer Festphase, die hauptsächlich Cadmiumsulfid enthält, und eine Abtrennung dieser Festphase ausgehend von einer wässrigen Alkalimetallsulfatlösung, aus welcher das Cadmium entfernt wurde, umfasst.
  14. Verfahren nach einem beliebigen der Ansprüche 6 und 7, dadurch gekennzeichnet, dass die co-Kristallisation ein Versetzen der cadmiumhaltigen wässrigen Lösung, aus welcher das Cadmium entfernt werden soll, mit einer Calciumverbindung umfasst, die dazu befähigt ist, in dieser Lösung einen Niederschlag von Calciumsulfat-Anhydrit und/oder-Halbhydrat zu bilden.
  15. Verfahren nach Anspruch 14, dadurch gekennzeichnet, dass es eine Wiederverwertung der Festphase auf Basis von Calciumsulfat-Dihydrat mit verringertem Cadmiumgehalt bei der co-Kristallisation umfasst, und zwar als Calciumverbindung gemäß den obigen Ausführungen.
EP20070726637 2007-03-06 2007-03-06 Verfahren zur verarbeitung von cadmiumhaltigen feststoffen Active EP2132347B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL07726637T PL2132347T3 (pl) 2007-03-06 2007-03-06 Sposób obróbki kadmonośnych substancji stałych

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/EP2007/052066 WO2008113403A1 (fr) 2007-03-06 2007-03-06 Procede de traitement de solides cadmiferes

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Publication Number Publication Date
EP2132347A1 EP2132347A1 (de) 2009-12-16
EP2132347B1 true EP2132347B1 (de) 2011-06-01

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EP20070726637 Active EP2132347B1 (de) 2007-03-06 2007-03-06 Verfahren zur verarbeitung von cadmiumhaltigen feststoffen

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EP (1) EP2132347B1 (de)
AT (1) ATE511553T1 (de)
ES (1) ES2367217T3 (de)
PL (1) PL2132347T3 (de)
WO (1) WO2008113403A1 (de)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3117476B1 (fr) 2020-12-10 2023-04-21 Ocp Sa Procede integre de decadmiation d’acide phosphorique

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL8601846A (nl) * 1986-07-15 1988-02-01 Stamicarbon Werkwijze voor het verwijderen van zware metalen uit zure fosfaathoudende waterige media.
IL85751A (en) * 1988-03-16 1991-12-15 Negev Phosphates Ltd Method for the removal of heavy metal ions from phosphoric acid
FR2649391B1 (fr) * 1989-07-04 1991-10-31 Pierre Becker Procede de traitement de l'acide phosphorique pour en eliminer certains metaux lourds
TNSN92119A1 (fr) * 1992-02-07 1993-06-08 Ct D Etudes Et De Rech S Des Phosphates Mineraux Cerphos Procede de fabrication d'acide phosphorique marchand a tres basse teneur en cadmium
MA23803A1 (fr) * 1996-02-06 1996-10-01 Cerphos Nouveau procede de decadmination d'acide phosphorique

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WO2008113403A1 (fr) 2008-09-25
PL2132347T3 (pl) 2011-12-30
EP2132347A1 (de) 2009-12-16
ATE511553T1 (de) 2011-06-15
ES2367217T3 (es) 2011-10-31

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